Raman spectroscopy has been used to characterise both organic and geological samples in order to build a database for the future characterization of biomarker molecules that are of astrobiological relevance. Characteristic geological features and hydrated minerals recently found on the surface of Mars by the NASA planetary rovers Spirit and Opportunity suggest that a possible biosphere could have once existed there. Analytical instrumentation protocols for the unequivocal detection of biomarkers in suitable geological matrices are critical for future unmanned explorations, including the forthcoming ESA ExoMars mission scheduled for 2018. Several geological features found on the surface of Mars by planetary rovers suggest that a possible extinct biosphere could exist based on similar sources of energy as occurred on Earth. For this reason, analytical instrumental protocols for the detection of isolated biomarkers preserved in suitable geological matrices unequivocally and non-destructively have to be evaluated for future unmanned missions. Raman spectroscopy is currently part of the Pasteur instrumentation suite of the ExoMars mission for the remote detection of extant or extinct life signatures in the Martian surface and subsurface. Terrestrial analogues of Martian sites have been identified and the biogeological modifications resulting from extremophilic survival activity have been studied. Here we present the Raman spectral characterization of several examples of organic compounds which have been recorded using 785 nm, 633 nm and 514 nm laser excitation -polycyclic aromatic hydrocarbons (PAHs), organic acids, chlorophyll and carotenoids. Experimental mixtures of ß-carotene in usnic acid, PAHs in usnic acid and PAHs in mineral matrices have also been investigated. Organic compounds and PAHs located under crystalline minerals samples were identified using a 5x objective lens and 785 nm III excitation. The pure compounds and compound mixtures were also analysed using X-ray powder diffraction and scanning electron microscopy (SEM). The results of this study indicate that near infrared laser at 785 nm provided the clearest and the most informative spectra due to the reduction of fluorescence emission. Higher energy lasers operating in the visible region have resulted in the emission of significant background fluorescence. Few samples fluoresce even with the use of 785 nm excitation and FT-Raman spectroscopy remains the instrument of choice for the analysis of these samples.

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Master / Master of Philosophy

No description available.

The mechanisms of the deterioration of cellulose acetate compounded with triphenyl phosphate were investigated. A key peak shift of 726cm⁻¹ to 718cm⁻¹ in the Raman spectrum of triphenyl phosphate (726cm-1 uncompounded) when compounded in cellulose acetate (718cm⁻¹) was tied to the action of C-O bonds in triphenyl phosphate. The molecular bonds responsible for the 726cm⁻¹ peak were identified by collecting and examining spectra of chemicals with functional groups similar to triphenyl phosphate. Initially it was hypothesized that triphenyl phosphate acts as nucleophilic catalyst of deacetylation. This mechanism was evaluated by dissolving triphenyl phosphate in solvents that served as functional group analogues of cellulose acetate. These liquid-solution systems have a faster rate of reaction and complete mixing with triphenyl phosphate compared with what is seen in cellulose acetate solid-solution systems. The results of the cellulose acetate analogue experiments did not support the hypothesis of triphenyl phosphate acting as a nucleophilic catalyst of deacetylation. The results instead support a new theory of deterioration induced by the recrystallization of triphenyl phosphate. Additionally, the prevailing theory of triphenyl phosphate induced deterioration as proposed by Shinagawa et al. in 1992 was reviewed. The experiments conducted here do not support Shinagawa's theory.

No description available.

No description available.

This thesis addresses various issues in U-Pb zircon geochronology, proposing new experimental protocols in conventional chemical abrasion-isotope dilution thermal ionization mass spectrometry or CA-(ID)-TIMS and developing a new method for Pb evaporation-condensation from zircon that allows high precision Pb-Pb age determination on Precambrian samples. Various experiments are also done on zircon to extract U-Pb information by in situ flux aided fusion methods and to optimize a better silica gel Pb-ionization activator. Radiation damage caused by U decay in zircon disrupts its ‘closed system’ behavior leading to the loss of daughter radiogenic Pb and resulting in inaccurate ages. A high temperature thermal annealing procedure has been proposed to prevent such Pb loss. Studies presented here have been carried out using Laser Raman Spectroscopy and Scanning Electron Microscopy to characterize radiation damage and effects of laboratory induced thermal annealing on such damage. Backscattered electron images reveal a variety of textures for ZrO2 overgrowths on zircon annealed at 1450oC. Highly damaged zircon produces finer polycrystalline aggregates (<5µm) than zircon with less damage. Raman spectroscopy indicates that crystals with different levels of radiation damage are only partially restored by annealing at 1000oC for 2–3 or 20 days. Annealing at 1450oC for 1 h results in partial breakdown of zircon but restores Raman peak widths and wave numbers. Raman spectra are much less sensitive to polarization angle for annealed highly damaged grains than for weakly damaged zircon showing that when highly damaged zircon is recrystallized, it becomes a polycrystalline aggregate that pseudomorphs the original single crystal. The whole grain Pb evaporation-condensation method is based on 206Pb-207Pb age analyses where zircon grains are pre-treated at 1450oC to drive out all disturbed Pb and then they are kept at 1600oC for an hour or two during which Pb atoms are evaporated out of the grain and deposited directly into a clean Savillex teflon vial or a wide Re filament. This technique allows the use of a 202Pb-205Pb double spike for precise isotopic fractionation correction. Examples are shown in which application of this technique to zircon from Precambrian samples has successfully yielded sub-million year age precisions.